Rosin amine anti-fouling agents

ABSTRACT

The invention relates to new and known compounds as well as methods for preventing the attachment of aquatic organisms to surfaces which are submerged for extensive periods of time in water. More particularly, this invention relates to the protection of submerged surfaces with new isonitrile, formamide, isocyanate and isothiocyanate anti-fouling agents.

FIELD OF INVENTION

The invention relates to new and known compounds as well as methods forpreventing the attachment of aquatic organisms to surfaces which aresubmerged for extensive periods of time in water. More particularly,this invention relates to the protection of submerged surfaces with newisonitrile, formamide, isocyanate and isothiocyanate anti-foulingagents.

BACKGROUND OF THE INVENTION

The ever recurring growth of fouling organisms on underwater structuressuch as ships, docks, piers, pilings, fishnets, heat exchangers, dams,piping structures, intake screens, cooling towers and the like is acostly and hazardous problem in both marine and freshwater endeavors.The presence of fouling organisms such as barnacles, zebra mussels,algae, diatoms, hydroids, bryozoa, ascidians, tubeworms, Asiatic clamsand the like causes economic damage in various ways: for example,attachment to the hulls of ships reduces fuel efficiency and causes lossof profitable sailing time because of the need to clean the hulls.Similarly, the attachment of these organisms to cooling water equipmentdecreases heat conductivity which eventually reduces or block thecooling power of the equipment and drives up cost.

A variety of agents useful for controlling fouling organisms in freshwater or sea water have been used to prevent the attachment andovergrowth of these organisms. A common method of controlling thepresence or attachment of fouling organisms is to coat or permeate theunderwater structure with a composition which comprises mixtures oftoxic compounds such as tri-n-butyl tin or copper compounds.Anti-fouling agents in the form of a paint can contain up to 60% byweight of the active ingredients and can be used to paint surfaces suchas the hull of ships. The paint prevents attachment and growth offouling organisms by continuously releasing anti-fouling agentsunderwater. The disadvantage of many of the present anti-fouling agentsis that they are persitant in the environment, are often acutely toxicand degrade too slowly in aquatic environments and are, therefore,ecologically harmful. Hazardous anti-fouling agents can eventuallybioaccumulate and enter the food chain and therefore represent a threatto marine and human life.

For example, it is well established that heavy metal compounds,especially organotin compounds that are widely used as anti-foulingagents, accumulate in mussels.

It is an object of this invention to provide an environmentally andecologically sound method of combatting or controlling marine andfreshwater fouling organisms.

It is another object of this invention to provide an effective methodfor protecting aquatic structures against fouling by marine orfreshwater fouling organisms.

It is a further object of this invention to provide antifoulantcompositions which comprises certain derivatives of rosin compounds asthe active agents.

SUMMARY OF THE INVENTION

The present invention provides new and known compounds and a method toprevent settlement on surfaces by marine or freshwater fouling organismwhich comprises contacting said organism or the locus thereof with ananti-fouling-effective amount of at least one compound of formula I1–I13

wherein

-   R¹ represents NR²R³ wherein    -   R² represents a hydrogen atom, C1–C8-alkyl and    -   R³ represents C═OR⁴ wherein    -   R⁴ represents a hydrogen atom or one of the groups OR⁵ or NHR⁵        wherein    -   R⁵ designates C1–C8-alkyl or aryl, each optionally substituted        by halogen; or-   R¹ represents N═CR⁶R⁷ wherein    -   R⁶ represents a hydrogen atom, C1–C6-alkyl or aryl, and    -   R⁷ represents C1–C6-alkyl or aryl, each optionally substituted        by halogen; or-   R¹ represents an isonitrile, isocyanate, isothiocyanate or a    guanidino group; and-   n represents 0 or 1.

In the specification and claims the term:

-   halogen has the meaning of C1, Br, I or F;-   alkyl has the meaning of straight-chain or branched alkyl with 1 to    8, preferably 1 to 4 carbon atoms;-   aryl has the meaning of aromatic, mono- or polycyclic hydrocarbon    rings such as for example and preferred: naphthyl, anthranyl,    phenanthryl, especially phenyl.

Preferred are compounds of formula I1–I13 wherein

-   R¹ represents NR²R³ wherein    -   R² represents a hydrogen atom or C1–C4-alkyl and    -   R³ represents C═OR⁴ wherein    -   R⁴ represents a hydrogen atom or one of the groups OR⁵ or NHR⁵        wherein    -   R⁵ represents C1–C4-alkyl or aryl, each optionally substituted        by halogen; or-   R¹ represents N═CR⁶R⁷ wherein    -   R⁶ represents a hydrogen atom, methyl or optionally halogen        substituted aryl, and    -   R⁷ represents C1–C4-alkyl or optionally halogen substituted        aryl; or-   R¹ represents an isonitrile, isocyanate, isothiocyanate or guanidino    moiety.

Especially preferred are compounds of formula I1–I13 wherein

-   R¹ represents NR²R³ wherein-   R² represents a hydrogen atom and-   R³ represents C═OR⁴ wherein-   R⁴ represents a hydrogen atom.

Especially preferred are also compounds of formula I1–I13 wherein

-   R¹ represents NR²R³ wherein-   R² represents a hydrogen atom and-   R³ represents C═OR⁴ wherein-   R⁴ represents OR⁵ or NHR⁵ wherein-   R⁵ represents methyl, ethyl, n- or i-propyl or n-, s-, i- or    t-butyl, or phenyl which is optionally substituted by halogen.

Especially preferred are also compounds of formula I1–I13 wherein

-   R¹ represents N═CR⁶R⁷ wherein-   R⁶ represents methyl, ethyl, n- or i-propyl, n-, s-, i- or t-butyl,    or preferred a hydrogen atom or and-   R⁷ represents methyl, ethyl, n- or i-propyl, n-, s-, i- or t-butyl    or phenyl.

Especially preferred are also compounds of formula I1–I13 wherein

-   R¹ represents an isonitrile, isocyanate, isothiocyanate or guanidino    moiety.

Preferred are compounds wherein n represents 1.

Preferred are Compounds of the Formula I8

The aforementioned compounds are accessible by standard procedures oforganic chemistry which can be adopted to the Rosin moiety. The startingRosin derived from Tall Oil, Gum or Wood is commercially available; forexample Rosin amine as Hercules® Amine D. An overview on the differentisomers of abietic acid as well as their preparation is given byGang-Fung Chen in Progress in Organic Coatings 20, 1992, 139–167. In thefollowing general schemes the synthesis of the different Rosin aminederivatives is outlined. For reasons of simplification, the synthesisroutes are outlined for substructure I8 with n=1. The reaction sequencescan be adopted easily to the other pure isomers and rosinoxidation/reduction products and also to mixtures of them.

Scheme 1

Compounds of formula I8 are accessible via acylation of Rosin amine witha chloro-formic-ester in an inert solvent with a base as HCl acceptor(see: Houben-Weyl Vol. 8, 1952, 137–140; ibid. Vol. 11/2, 1958, 27–37).

Scheme 2

Ureas of formula III can be synthesized by reacting Rosin amine with anisocyanate in an inert solvent (benzene, toluene, hydrocarbons etc.);see: Houben-Weyl Vol. E4, 1983, 352–357 or alternatively via reaction ofRosin isocyanate (s. below) with an aliphatic or aromatic amine.

Scheme 3

Schiff-bases of Rosin amine are accessible via condensation of Rosinamine with an aldehyde or keton (Houben-Weyl Vol. 11/2, 1958, 74 –85).

The synthesis of Rosin isocyanide has been published (T. Ohsawa et al.,Tetrahedron Lett., 1989, 845–846).

Rosin isothiocyanate (CAS-Nr.: 115 269–93–7) can be synthesized fromRosin amine through reaction with thiophosgene (see analogous sequencewith phosgene: Ozaki, Chem Rev. 72, 457–460), or alternatively with athiophosgene substitute, namely thiocarbonyl-diimidazole (see example3).

The preparation of Rosin isocyanate has been described (E. Corey et al.,Tetrahedron Lett. 1981, 299–302).

In the case of compounds of formula 1 with n=0, the required startingmaterial Dehydroabietan-1-yl-amine can be obtained according to Stockelet al., Can. J. Chem. 1963, 834–836.

The synthesis of Dehydroabietan-1-yl-isocyanate is described in Chem.Pharm. Bull. 1985, 1472–1487.

All other derivatives (formula I, n=0) can be synthesized in analogousmanner as described for Rosin amine.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

A fouling organism which may be combatted or controlled by the method ofthe invention can be any marine or freshwater organism which can attachto an inner or outer surface of a structure which is submerged or incontinual contact with water. Examplary organisms include algae,including members of the phyla Chlorophyta, Pharophyta and Rhodophyta;tunicates, including members of the class Ascidiacea such as Cionaintestinalis, Diplosoma listerianium and Botryllus sclosseri, andmembers of the class Hydrozoa including Clava squamata, Hydractiniaechinata, Obelia geniculata and Tubularia larynx;

-   Bivalves including Mytilus edulis, Cassostrea virginica, Ostrea    edulis, ostrea chilensia, Lasaea rubra and members of the family    Dreissenidae (or zebra mussels) and members of the family    Corbuculidae (or Asiatic clams), bryozoans including Electra pilosa,    Conopeum reticulatum, Bugula neritina and Bowerbankia gracilis;-   Polychaete worms including Hydroides norvegica, Pomatoceros    triqueter, Mercierella enigmata and Spirorbis spp.;-   Sponges and members of the class Cirripedia (barnacles) such as    Balanus amphitrite, Lepas anatifera, Balanus balanus, Balanus    balanoides, Balanus hameri, Balanus creatus, Balanus improvisus,    Balanus ga/eatus, Balanus eburneus, Elminius modestus, Balanus    tulipiformis and Balanus perforatus.

Organisms of the genus Balanus are frequent foulers of aquaticstructures. Specific fouling organisms to which this invention isespecially directed include barnacles, zebra mussels, algae, diatoms,hydroids, bryozoa, ascidians, tube worms and asiatic clams, but also thebacterial slime.

Among the aquatic structures which may be protected by the method ofinvention are any submerged or partially submerged structure, eithermobile or stationary, such as fishnet, boat, ship, piling, coolingtower, pipeline, standpipe, heat exchanger, dam, intake screen or thelike.

In actual practice compound of formula I1–I13 may be brought intocontact with a fouling organism by:

-   -   coating the aquatic structure to be protected with an        antifouling-effective amount of said Rosin Amine derivative such        that the antifouling compound is released at the to be protected        surface area into the aquatic environment immediately.    -   including an antifouling-effective amount of the Rosin Amine        Derivative within material formed into an aquatic structure        which then releases said compound,    -   releasing an antifouling-effective amount of said compound        directly into the aquatic environment surrounding the structure        to be protected, or any other method wherein the Rosin Amine        Derivative comes in contact with the fouling organism.

The amount of Rosin Amine Derivative to be used in the method ofinvention will vary according to the specific compound used, theidentity of the fouling organism to be controlled, degree of foulingpressure of the surrounding aquatic environment, the water temperature,the mode of contact and the like.

The Rosinamine derivatives can be used as individual active compounds orelse in combination with active compounds usually employed in theanti-fouling sector. These can preferably be heavy metals, such as Cu,or heavy metal compounds, such as, for example, bis(trialkyltin)sulphides, tri-n-butyl laurate, tri-n-butyl chloride, copper(I) oxide,triethyltin chloride, tri-n-butyl(2-phenyl-4-chlorophenoxy)-tin,tri-butylin oxide, molybdenum disulfide, antimony oxide, polymeric butyltitanate, phenyl-(bispyridine)-bismuth chloride, tri-n-butyltinfluoride, manganese ethylenebisdithiocarbamate, zincdimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, the zinc saltor copper salt of 2-pyridinethiol-1-oxide,bisdimethyldithiocarbamoyl-zinc ethylenebisdithiocarbamate, zinc oxide,copper(I) ethylene-bis-dithiocarbamate, copper thiocyanate, coppernaphthenate and tributyltin halides.

The action spectrum of the rosinamine derivatives is extended further orparticular effects are achieved by these combinations of activecompounds. Synergistic effects are obtained in many cases. Thesynergistic effect manifests itself particularly clearly if the activecompound combinations are present in certain weight ratios. However, theweight ratios of the active compounds in the active compoundcombinations can vary within a relatively wide range.

Preferred combination partners for the rosinamine derivatives arealgicides, such as diuron, dichlorophen, endothal, fentin acetate orquinoclamine, molluscicides, such as fentin acetate, metaldehyde,methiocarb, niclosamide, thiodicarb and trimethacarb, fungicides, suchas dichlofluanid, tolylfluanid, iodopropargyl butylcarbamate,fluorfolpet and azoles, such as propiconazole, metconazole,cyproconazole and tebuconazole or conventional antifouling activecompounds, such as 2-(N,N-dimethylthiocarbamoylthio)-5-nitrothiazyl,tetrabutyldistannoxane,2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine,4,5-dichloro-2-n-octyl-4-isothiazolin-3-one,2,4,5,6-tetrachloroisophthalodinitril, tetramethylthiuram disulphide,2,4,6-trichloro-phenylmaleimide,2,3,5,6-tetrachloro-4-(methylsulphonyl)-pyridine, diiodomethyl-paratrylsulphone, thiabendazol, tetraphenyl-boron-pyridin salt, and the copperand sodium salt of 2-pyridinethiol-1-oxide.

The anti-fouling composition preferably comprises the rosinaminederivatives in concentrations of 0.5 to 60% by weight, preferablybetween 1 to 25% by weight.

Compositions of the invention comprise an aquatically acceptable inertcarrier and an antifouling-effective amount of a Rosin Amine Derivativeof formula I. For application onto structural surfaces, preferredcompositions of the invention include a film-forming component such as apolymer resin solution. Exemplary polymer resins include unsaturatedpolyester resins formed from: a) unsaturated acids or anhydrides, suchas maleic anhydride, fumaric acid, itaconic acid and the like; b)saturated acids or anhydrides, such as phthalic anhydride, isophthalicanhydride, terephthalic anhydride, tetrahydrophthalic anhydride,tetrahalophthalic anhydride, adipic acid, subacic acid, and the like; c)glycols, such as ethylene glycol, and the like; d) vinyl monomers, suchas styrene, vinyl toluene, chlorostyrene, bromostyrene, acrylates likemethylmethacrylate, ethylene glycol dimethacrylate and the like. Othersuitable resins include vinyl ester-, vinyl acetate-, and vinylchloride-based resins, elastomeric components, vulcanized rubbers,rosins, metalresinates and urethane-based resins.

For further description of components common in antifouling paints seeUngerer in Chem. Ind. 1985, 37, 730–732 and Williams in AntifoulingMarine Coatings, Noves, Park Ridge, 1973.

EXAMPLE 1 N-Formyl-rosinamine (1)

The starting material Rosinamine (Hercules® Amine D) is a mixture ofprimary amines derived from modified Rosin. It is described asdehydroabietylamine of technical grade and was used in the followingsyntheses without further purification.

To a solution of Rosin amine in ethyl acetate 5 equiv. of ethyl formateare added at room temperature under continuous stirring. After 16 h atrt, the solvent is evaporated to dryness and the residue is filteredthrough a short column of silica gel to furnish N-formyl rosin amineunder the form of a compact resin (yield: 86%). Characterisation:visqueous oil; ¹H-NMR, δ(ppm): 7.94–8.23(1H); 7.15 (1H); 6.99 (1H); 6.89(1H); 5.46 (1H); 2.76–3.27 (5H); 1.22 (6H); 1.21 (3H); 0.95 (3H).

EXAMPLE 2 Rosin Isocyanide (2)

Diisopropylarine (2.7 equiv.) and phosphorous oxychloride (1.1 equiv.)were successively added dropwise to a stirred solution of N-formylrosinamine in dichloromethane at 0° C. under an atmosphere of drynitrogen. After 1 h at 0° C., a 20% solution of sodium carbonate wasadded and the reaction mixture was allowed to reach room temperature for1 h. 20% sodium carbonate and water were added, extraction of theaqueous phase with dichloromethane followed by filtration of the residuethrough a column of silica gel furnished Rosin isocyanide as acolourless oil (yield: 85%).

Characterisation: visqueous oil; ¹H NMR, δ(ppm): 7.16 (1H); 7.00 (1H);6.88 (1H); 2.76–3.34 (5H); 1.22 (6H); 1.21 (3H); 0.98 (3H).

EXAMPLE 3 Rosin Isothiocyanate (3)

A solution of thiocarbonyl diimidazole (1.5 equiv.) in dichloromethanewas added to a stirred solution of Rosinamine in dichloromethane at 0°C. under an atmosphere of dry nitrogen. After the addition was complete,the reaction mixture was heated at 45° C. during 16 h. The solvent wasevaporated and the solid residue filtered through a column of silica gelto furnish Rosinisothiocyanate as an oil (yield: 87%). Characterisation:oil; ¹H-NMR, δ(ppm): 7.16 (1H); 6.99 (1H); 6.89 (1H); 3.37 (2H); 2.90(2H); 2.82 (1H); 1.22 (6H); 1.21 (3H); 0.96 (3H).

Evaluation of Marine Antifouling Activity of Test Compounds

The rate of settlement of laboratory reared cyprid larvae of thebarnacle Balanus amphitrite was determined for testing the activity ofcandidate anti-fouling compounds.

Settlement Assay

Tests are carried out in four replicates in sterile polystyrene multiwell plates. Between 25 and 40 cyprid larvae are injected in the dishescontaining either 2 ml of test solution (see below), solvent control ora positive control (Dichloro-n-octyl-isothiazolinone).

Dishes are incubated for 24 h at a temperature of 27° C.±2. Afterincubation the cyprids are screened for signs of toxicity. Larvae areclassified in three categories: A) alive and swimming; B) alive but notactive; C) dead. The test is terminated by addition of a drop of 20%formaldehyde and the numbers of settled and non-settled larvae arecounted.

Settlement is evaluated as follows: 1) Non settled: not attached freeswimming cyprids; 2) settled cyprids: attached, but not metamorphosedcyprids; 3) barnacles: attached juvenile barnacles.

Categories 2 and 3 are considered to be settled. Percentage settlementin test solution is compared with controls. Estimates of the medianeffect concentration (EC-50) after 50 hrs. are calculated using theSpearman-Kärber method.

All seawater used is of natural origin and filtered unto 0.2 micron.Stock solutions of test compounds are prepared by dissolving an amountof test substance in a suitable solvent and subsequent addition ofseawater.

The stock solutions are used to prepare several dilution series inseawater. Controls are made of seawater, or, if appropriate, in amixture of seawater and solvent. The solvent concentration in thecontrols is equal to the highest concentration in the test solution. Asan internal standard (positive control) a concentration range of 0 to 5ppm dichloro-n-octylisothiazolinone will is included in each test.

Test Results Compound EC50 for settlement inhibition in ppm 1 2.6 2 0.12reference* 0.37 *≡ 4,5-dichloro-n-octylisothiazolinone

1. A compound selected from the group consisting of compounds having theformulae 11, 12, 13, 15, 16, 17, 18, 19, 110, 111, 112, and 113:

wherein R¹ represents NR²R³ wherein R² represents a hydrogen atom or aC1–C8-alkyl and R³ represents C═OR⁴ wherein R⁴ represents a hydrogenatom or one of the groups OR⁵ or NHR⁵ wherein R⁵ designates aC1–C8-alkyl or aryl, each optionally substituted by halogen; or R¹represents N═CR⁶R⁷ wherein R⁶ represents a hydrogen atom or aC1–C6-alkyl or aryl, and R⁷ represents a C1–C6-alkyl or aryl, eachoptionally substituted by halogen; or R¹ represents an isonitrile,isocyanate, isothiocyanate or guanidino group; and n represents 0 or 1and wherein when R¹ is isothiocyanate, n is
 0. 2. The compound accordingto claim 1, wherein R¹ represents NR²R³, and wherein R² represents ahydrogen atom or a C1–C4-alkyl and R³ represents C═OR⁴ wherein R⁴represents a hydrogen atom or one of the groups OR⁵ or NHR⁵ wherein R⁵represents a C1–C4-alkyl or aryl, each optionally substituted byhalogen; or R¹ represents N═CR⁶R⁷ wherein R⁶ represents a hydrogen atom,methyl or optionally halogen substituted aryl, and R⁷ represents aC1–C4-alkyl or optionally halogen substituted aryl; or R¹ represents anisonitrile, isocyanate, isothiocyanate or guanidino moiety.
 3. Thecompound according to claim 1, wherein R¹ represents NR²R³ wherein R²represents a hydrogen atom and R³ represents C═OR⁴ wherein R⁴ representsa hydrogen atom.
 4. The composition according to claim 1, wherein R¹represents NR²R³ wherein R² represents a hydrogen atom or a C1 —C4-alkyland R³ represents C═OR⁴ wherein R⁴ represents a hydrogen atom or one ofthe groups OR⁵ or NHR⁵ wherein R⁵ represents a C1 —C4-alkyl or aryl,each optionally substituted by halogen; or R¹ represents N═CR⁶R⁷ whereinR⁶ represents a hydrogen atom, methyl or optionally halogen substitutedaryl, and R⁷ represents a C1–C4-alkyl optionally halogen substitutedaryl; or R¹ represents an isonitrile, isocyanate, isothiocyanate orguanidino moiety.
 5. A method for controlling or combatting a marine orfreshwater fouling organism comprising contacting said organism or thelocus thereof with an anti-fouling-effective amount of at least oneselected from the group consisting of compounds having the formulae 11,12, 13,, 15, 16, 17, 18, 19, 110, 111, 112, and 113:

wherein R¹ represents NR²R³ wherein R² represents a hydrogen atom or aC1–C8-alkyl and R³ represents C═OR⁴ wherein R⁴ represents a hydrogenatom or one of the groups OR⁵ or NHR⁵ wherein R⁵ designates aC1–C8-alkyl or aryl, each optionally substituted by halogen; or R¹represents N═CR⁶R⁷ wherein R⁶ represents a hydrogen atom or aC1–C6-alkyl or aryl, and R⁷ represents a C1–C6-alkyl or aryl, eachoptionally substituted by halogen; or R¹ represents an isonitril,isocyanate, isothiocyanate or guanidino group; and n represents 0 or 1.6. An agent comprising an antifouling-effective amount of at least onecompound and an aquatically acceptable inert carrier, wherein thecompound is selected from the group consisting of compounds having theformulae 11, 12, 13, 15, 16, 17, 18, 19, 110, 111, 112, and 113:

wherein R¹ represents NR²R³ wherein R² represents a hydrogen atom or aC1–C8-alkyl and R³ represents C═OR⁴ wherein R⁴ represents a hydrogenatom or one of the groups OR⁵ or NHR⁵, wherein R⁵ designates aC1–C8-alkyl or aryl, each optionally substituted by halogen; or R¹represents N═CR⁶R⁷ wherein R⁶ represents a hydrogen atom or aC1–C6-alkyl or aryl, and R⁷ represents a C1 —C6-alkyl or aryl, eachoptionally substituted by halogen; or R¹ represents an isonitril,isocyanate, isothiocyanate or guanidino group; and n represents 0 or 1.7. The agent of claim 6, wherein the agent comprises 0.5 to 60% byweight of said compound.
 8. A method for controlling and combatting amarine fouling organism, a freshwater fouling organism, or combinationsthereof, the method comprising treating the organism with a compoundselected from the group consisting of compounds having the formulae 11,12, 13, 15, 16, 17, 18, 19, 110, 111, 112, and 113:

wherein R¹ represents NR²R³ wherein R² represents a hydrogen atom or aC1–C8-alkyl and R³ represents C═OR⁴ wherein R⁴ represents a hydrogenatom or one of the groups OR⁵ or NHR⁵ wherein R⁵ designates a C1—C8-alkyl or aryl, each optionally substituted by halogen; or R¹represents N═CR⁶R⁷ wherein R⁶ represents a hydrogen atom or aC1–C6-alkyl or aryl, and R⁷ represents a C1–C6-alkyl or aryl, eachoptionally substituted by halogen; or R¹ represents an isonitril,isocyanate, isothiocyanate or guanidino group; and n represents 0 or 1.9. The method of claim 8, wherein the organism is treated with an agentcomprising an antifouling-effective amount of the compound and anaquatically acceptable inert carrier.
 10. A process for preparing ananti-fouling agent comprising mixing a compound with an aquaticallyacceptable inert carrier, wherein the compound is selected from thegroup consisting of compounds having the formulae 11, 12, 13, 15, 16,17, 18, 19, 110, 111, 112, and 113:

wherein R¹ represents NR²R³ wherein R² represents a hydrogen atom or aC1–C8-alkyl and R³ represents C═OR⁴ wherein R⁴ represents a hydrogenatom or one of the groups OR⁵ or NHR⁵ wherein R⁵ designates aC1–C8-alkyl or aryl, each optionally substituted by halogen; or R¹represents N═CR⁶R⁷ wherein R⁶ represents a hydrogen atom or aC1–C6-alkyl or aryl, and R⁷ represents a C1 —C6-alkyl or aryl, eachoptionally substituted by halogen; or R¹ represents an isonitril,isocyanate, isothiocyanate or guanidino group; and n represents 0 or 1.11. An agent comprising an antifouling-effective amount of at least onecompound and a film forming polymer resin, wherein the compound isselected from the group consisting of compounds of claim 1 having theformulae 11, 12, 13, 15, 16, 17, 18, 19, 110, 111, 112, and 113:


12. The agent of claim 11 wherein, the polymer is selected from thegroup consisting of unsaturated polyester resins formed from monomerscomprising: a) unsaturated acids or anhydrides, selected from the groupconsisting of maleic anhydride, fumaric acid, itaconic acid andadmixtures thereof; b) saturated acids or anhydrides, selected from thegroup consisting of phthalic anhydride, isophthalic anhydride,terephthalic anhydride, tetrahydrophthalic anhydride, tetrahalophthalicanhydride, adipic acid, subacic acid, and admixtures thereof, c)glycols, selected from the group consisting of ethylene glycol, and thelike; d) vinyl monomers, selected from the group consisting of styrene,vinyl toluene, chlorostyrene, bromostyrene, acrylates selected from thegroup consisting of methylmethacrylate, ethylene glycol dimethacrylateand admixtures thereof vinyl ester-, vinyl acetate-, and vinylchloride-based resins; elastomeric components; vulcanized rubbers;rosins; metalresinates; and urethane-based resins.
 13. An agentcomprising an antifouling-effective amount of at least one compound andan algicide, wherein the compound is selected from the group consistingof compounds of claim 1 having the formulae 11, 12, 13, 15, 16, 17, 18,19, 110, 111, 112, and 113:


14. The agent of claim 13, where in the algicide is selected from thegroup consisting of diuron, dichlorophen, endothal, fentin acetate orquinoclamine, molluscicides, selected from the group consisting offentin acetate, metaldehyde, methiocarb, niclosamide, thiodicarb andtrimethacarb, fungicides, selected from the group consisting ofdichlofluanid, tolylfluanid, iodopropargyl butylcarbamate, fluorfolpetand azoles, selected from the group consisting of propiconazole,metconazole, cyproconazole and tebuconazole and antifouling activecompounds, selected from the group consisting of2-(N,N-dimethylthiocarbamoylthio)-5-nitrothiazyl,tetrabutyldistannoxane,2-tert-butylamino-4-cyclopropylamino-6-methyl-thio-1,3,5-triazine,4,5-dichloro-2-n-octyl-4-isothiazolin-3-one,2,4,5,6-tetrachloroisophthalodinitril, tetramethylthiuram disulphide,2,4,6-trichlorophenylmaleimide,2,3,5,6-tetrachloro-4-(methylsulphonyl)-pyridine, diiodomethyl-paratrylsulphone, thiabendazol, tetraphenyl-boron-pyridin salt, and the copperand sodium salt of 2-pyridinethiol-1-oxide.
 15. A compound selected fromthe group consisting of compounds having the formula 18,:

wherein R¹ represents NR²R³ wherein R² represents a hydrogen atom or aC1 —C8-alkyl and R³ represents C═OR⁴ wherein R⁴ represents a hydrogenatom or one of the groups OR⁵ or NHR⁵ wherein R⁵ designates aC1–C8-alkyl or aryl, each optionally substituted by halogen; or R¹represents N═CR⁶R⁷ wherein R⁶ represents a hydrogen atom or aC1–C6-alkyl or aryl, and R⁷ represents a C1–C6-alkyl or aryl, eachoptionally substituted by halogen; or R¹ represents an isonitrile,isothiocyanate or guanidino group; and n represents 0 or 1; or when R¹is isothiocyanate or isonitrile, then n is
 0. 16. A compound selectedfrom the group consisting of compounds having the formulae 11, 12, 13,15, 16, 17, 19, 110, 111, 112, and 113:

wherein R¹ represents NR²R³ wherein R² represents a hydrogen atom or aC1 —C8-alkyl and R³ represents C═OR⁴ wherein R⁴ represents a hydrogenatom or one of the groups OR⁵ or NHR⁵ wherein R⁵ designates aC1–C8-alkyl or aryl, each optionally substituted by halogen; or R¹represents NR²R wherein R² represents a C1–C8-alkyl and R³ representsC═OR⁴ wherein R⁴ represents a hydrogen atom or one of the groups OR⁵ orNHR⁵ wherein R⁵ designates a C1–C8-alkyl or aryl, each optionallysubstituted by halogen; or R¹ represents N═CR⁶R⁷ wherein R⁶ represents ahydrogen atom or a C₁–C₆-alkyl or aryl, and R⁷ represents a C1–C6-alkylor aryl, each optionally substituted by halogen; or R¹ represents anisonitrile, -isocyanate, isothiocyanate or guanidino group; and nrepresents 0 or 1; wherein when the formula is 11, and R1 is isocyanateor isothiocyanate then n=1.